CA1338497C - Latent polymerization initiator composition that is activated, after a delay time, by contact with air, and uses of such compositions - Google Patents
Latent polymerization initiator composition that is activated, after a delay time, by contact with air, and uses of such compositionsInfo
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- CA1338497C CA1338497C CA000610029A CA610029A CA1338497C CA 1338497 C CA1338497 C CA 1338497C CA 000610029 A CA000610029 A CA 000610029A CA 610029 A CA610029 A CA 610029A CA 1338497 C CA1338497 C CA 1338497C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
Abstract
Radical polymerizations are initiated by a combination initiator that comprises - N-alkyl-substituted tert-arylamines containing at least one aliphatic CH bond in the .alpha.-position;
- metal compounds that are at least partly soluble in the material to be initiated and that accelerate the drying of unsaturated oils; and - carboxylic acids having pKa values of no less than about 0.9 and is activated upon contact with oxygen from the air.
Polymerizable mixtures containing such a combination initiator may usefully be formulated as one part of multiple part adhesives, surface coatings, molding compounds, and the like that are storage stable in the absence of air, or even in the presence of air if formulated in at least two parts, with one of the above three parts of the initiator combination missing from each part.
- metal compounds that are at least partly soluble in the material to be initiated and that accelerate the drying of unsaturated oils; and - carboxylic acids having pKa values of no less than about 0.9 and is activated upon contact with oxygen from the air.
Polymerizable mixtures containing such a combination initiator may usefully be formulated as one part of multiple part adhesives, surface coatings, molding compounds, and the like that are storage stable in the absence of air, or even in the presence of air if formulated in at least two parts, with one of the above three parts of the initiator combination missing from each part.
Description
PATENT
1~38497 Docket D 8429 A LAT~NT POLYMERIZATION INITIATOR COMPO~ITION THA~ I8 ACTIVATED, AFTBR A D~LAY TIME, ~Y CONTACT ~IT~ AIR, AND
U8E8 OF ~UCH COMPO8ITION8 Field of the Invention This invention relates to new mixtures that react with the ambient natural atmosphere to produce, after a predictable delay time, an effective initiator for radical polymerization, particularly that of unsaturated materials such as acrylates and styrene. These latent polymerization initiator mixtures can usefully be combined with radically polymerizable materials to form mixtures which are sufficiently fluid to be readily shaped as desired and can be used, for example, as free-flowing or spreadable compositions or as pastes and then hardened under ambient conditions through initiation of the polymerization reaction. Such mixtures are useful in a very wide variety of applications, including for example adhesives, sealing compounds, the production of plastic objects by molding, and protective surface coatings formed by spreading air-hardenable fluids over surfaces, particularly solvent free paint systems and the like.
Statement of Related Art The peroxide- or hydroperoxide-initiated hardening of olefinically unsaturated compounds or mixtures generally requires in practice the presence, in addition to peroxy compounds, of materials called "activators", particularly when the reaction is to be initiated at low temperatures, for example at room temperature or only slightly elevated temperature. It is known that se'ected tertiary amine compounds partly aromatically substituted at the nitrogen atom perform such an activating function. Particularly common known activators for the initiation of polymeriza-tion reactions by benzoyl peroxide, for example, are 13~8497 dimethyl aniline and dimethyl-p-toluidine.
A totally different known class of activators for oxidative initiation of the polymerization of certain un-saturated materials, those called drying oils, are compounds, at least partly soluble in the material to be polymerized, of metals which can occur in more than one stable non-zero valence state and which accelerate the polymerization initiating reaction through shifts in valency during interaction with other components of the polymerizable mixture. Metal compounds such as these, sufficiently soluble in organic solvents and/or in binders, of metals of the type in question have long been known as so-called driers for the air drying of paints, varnishes and the like based on unsaturated oils. Sufficiently oil-soluble compounds of transition metals, which are capableof occurring in different valences, are particularly suitable for this purpose. The individual components differ in their ability to accelerate hardening, compounds of cobalt and/or manganese being particularly suitable, although iron also accelerates hardening. In addition to and, in particular, in combination with these highly active metallic components, it is possible to use comparable compounds of other metals which may also be capable of existing in different valences. A detailed description of such systems can be found, for example, in Ullmann, Encyklopadie der technischen Chemie, 4th Edition, Vol. 23 (1983), 421-424.
It is also known that the two types of promoters described here for the radical initiation of polymerization can lead by interaction to an enhanced effect. For exam-ple, an article by L. Horner et al, "Autoxidationsstudien an N,N-dialkylierten Anilinderivaten" (Autoxidation Studies on N,N-Dialkylated Aniline Derivatives), in Makromolekulare Chemie 93 (1966), pages 69 to 108, describes investigations into the acceleration of the spontaneous autoxidation of N-dialkyl-substituted aryl amine compounds in pure, highly dry ("superpure") oxygen gas. In the first stage of the 1~38497 ~ spontaneous autoxidation, an amine hydroperoxide compound is formed at aliphatic CH groups in the ~-position under the effect of dried, superpure oxygen. This spontaneous autoxidation of the ~,N-dialkylated arylamines takes place very slowly. According to the reference, the co-use of cobalt (II) compounds and, to a lesser extent, the co-use of iron (III) salts results in activation of the autoxida-tion process. In further studies reported in this reference, it is shown that acetic acid also has a pronounced accelerating effect on autoxidation of the tertiary amine compound whereas stronger acids, such as trichloroacetic acid, or mineral acids form true tertiary ammonium salts which are not autoxidizable. The use of cobalt ions in conjunction with acetic acid leads to the lS vigorously catalyzed autoxidation of dialkyl aniline compounds under the effect of superpure oxygen.
Finally, the reference cited above describes studies into the initiation of the polymerization of vinyl com-pounds by the dimethyl aniline/superpure oxygen/cobalt salt system. High-purity acrylonitrile, methyl methacrylate, ethyl acrylate and styrene can be polymerized with this system. The initiating reaction is interpreted as redox catalysis in which molecular oxygen acts as oxidizing agent. There are no references in the publication in question to the suitability of the multicomponent systems investigated for practical use in polymerization, and no such practical application is known to the present applicants, despite the availability of this reference for about twenty-five years.
It is an object of the present invention to provide a new class of activator systems which may be used in a new and simplified way for initiating the polymerization of olefinically unsaturated systems.
According to one aspect of the invention, a process of initiating the radical polymerization of olefinically unsaturated polymerizable components. The processcomprises rnixing the components with an activator system consisting essentially of:
~, .. ..
(a) from 30 to 60% by weight of a N-alkyl-substituted tertiary arylamine corresponding to formula I
R,~
= N - R3 (I) in which Rl is an unsubstituted or substituted aryl radical, R2 is an unsubstituted or substituted aryl radical or an unsubstituted or substituted, linear, or branched alkyl radical, and R3 is a substituted or unsubstituted linear or branched alkyl radical which has at least one H
atom in the a-position to the N;
(b) from 5 to 20% by weight of a metal compound which is soluble in said polymerizable components; and (c) from 30 to 60% by weight of a weakly acidic compound having a pKa value of at least about 0.9, all weights being based on the weight of said activator system, wherein the resultant mixture has an initial viscosity of at least between about 30 and about 100 mPa.s as measured at about 20 C with a Brookfield viscosimeter, and exposing the resulting ~ e to ambient air at room temperature or elevated temperature.
In another aspect of the invention, a filler may be added to the olefinically unsaturated polymerizable components prior to mixing the components with the activator system. In another embodiment, R1 is a phenyl radical and component (a) is an N, N-dialkyl-substituted aniline compound.
According to another aspect of the present invention, a moldable, radically-polymerizable, multi component mixture is provided. The mixture comprises olefinically unsaturated polymerizable components and an activator system consisting essentially of the three components (a), (b), and (c) described above.
In another aspect of the invention, component (c) of the mixture comprises at least one COOH group attached to preformed oligomer or polymer compounds.
~3 ~ ........
In yet another aspect of the invention, component (a) is kept separate from components (b) and (c) before mixing with the mixture of olefinically unsaturated polymerizable components.
Other and further aspects and advantages of the present invention will be apparent to those skilled in the art in view of the following detailed description.
Description of the Invention The new activator systems can be used to form mixtures wit~ olefinically unsaturated, poly~erizable components that do not polymerize in the absence of oxygen and water 3b _. ~
1338~97 are therefore stable in storage, either as one-part or multi-part adhesive systems. On the other hand, in a particularly important embodiment, these new adhesive systems can be activated, after a predictable time interval, usually called the ~pot life", by the action of water and oxygen always present in the ambient atmospheric air. Such adhesive systems will undergo time controlled hardening after the pot life has expired. In preferred embodiments, such activation occurs readily even at room temperature, although a moderate increase in temperature to as much as 30D C may sometimes be necessary.
In a first embodiment, the present invention includes radically polymerizable multicomponent mixtures that are sufficiently fluid to be shaped as desired, that are capable, simply by contact with ambient air at room temperature, of initiating radical polymerization of unsaturated molecules to produce time-controlled hardening after a predictable pot life, and that comprise, or preferably consist essentially of:
(A) ethylenically unsaturated, polymerizable molecules;
and (B) a polymerization initiator component that consists essentially of the following constituents:
(1) alkylaryl tertiary amine molecules containing at least one aliphatic N-C-H bond sequence;
1~38497 Docket D 8429 A LAT~NT POLYMERIZATION INITIATOR COMPO~ITION THA~ I8 ACTIVATED, AFTBR A D~LAY TIME, ~Y CONTACT ~IT~ AIR, AND
U8E8 OF ~UCH COMPO8ITION8 Field of the Invention This invention relates to new mixtures that react with the ambient natural atmosphere to produce, after a predictable delay time, an effective initiator for radical polymerization, particularly that of unsaturated materials such as acrylates and styrene. These latent polymerization initiator mixtures can usefully be combined with radically polymerizable materials to form mixtures which are sufficiently fluid to be readily shaped as desired and can be used, for example, as free-flowing or spreadable compositions or as pastes and then hardened under ambient conditions through initiation of the polymerization reaction. Such mixtures are useful in a very wide variety of applications, including for example adhesives, sealing compounds, the production of plastic objects by molding, and protective surface coatings formed by spreading air-hardenable fluids over surfaces, particularly solvent free paint systems and the like.
Statement of Related Art The peroxide- or hydroperoxide-initiated hardening of olefinically unsaturated compounds or mixtures generally requires in practice the presence, in addition to peroxy compounds, of materials called "activators", particularly when the reaction is to be initiated at low temperatures, for example at room temperature or only slightly elevated temperature. It is known that se'ected tertiary amine compounds partly aromatically substituted at the nitrogen atom perform such an activating function. Particularly common known activators for the initiation of polymeriza-tion reactions by benzoyl peroxide, for example, are 13~8497 dimethyl aniline and dimethyl-p-toluidine.
A totally different known class of activators for oxidative initiation of the polymerization of certain un-saturated materials, those called drying oils, are compounds, at least partly soluble in the material to be polymerized, of metals which can occur in more than one stable non-zero valence state and which accelerate the polymerization initiating reaction through shifts in valency during interaction with other components of the polymerizable mixture. Metal compounds such as these, sufficiently soluble in organic solvents and/or in binders, of metals of the type in question have long been known as so-called driers for the air drying of paints, varnishes and the like based on unsaturated oils. Sufficiently oil-soluble compounds of transition metals, which are capableof occurring in different valences, are particularly suitable for this purpose. The individual components differ in their ability to accelerate hardening, compounds of cobalt and/or manganese being particularly suitable, although iron also accelerates hardening. In addition to and, in particular, in combination with these highly active metallic components, it is possible to use comparable compounds of other metals which may also be capable of existing in different valences. A detailed description of such systems can be found, for example, in Ullmann, Encyklopadie der technischen Chemie, 4th Edition, Vol. 23 (1983), 421-424.
It is also known that the two types of promoters described here for the radical initiation of polymerization can lead by interaction to an enhanced effect. For exam-ple, an article by L. Horner et al, "Autoxidationsstudien an N,N-dialkylierten Anilinderivaten" (Autoxidation Studies on N,N-Dialkylated Aniline Derivatives), in Makromolekulare Chemie 93 (1966), pages 69 to 108, describes investigations into the acceleration of the spontaneous autoxidation of N-dialkyl-substituted aryl amine compounds in pure, highly dry ("superpure") oxygen gas. In the first stage of the 1~38497 ~ spontaneous autoxidation, an amine hydroperoxide compound is formed at aliphatic CH groups in the ~-position under the effect of dried, superpure oxygen. This spontaneous autoxidation of the ~,N-dialkylated arylamines takes place very slowly. According to the reference, the co-use of cobalt (II) compounds and, to a lesser extent, the co-use of iron (III) salts results in activation of the autoxida-tion process. In further studies reported in this reference, it is shown that acetic acid also has a pronounced accelerating effect on autoxidation of the tertiary amine compound whereas stronger acids, such as trichloroacetic acid, or mineral acids form true tertiary ammonium salts which are not autoxidizable. The use of cobalt ions in conjunction with acetic acid leads to the lS vigorously catalyzed autoxidation of dialkyl aniline compounds under the effect of superpure oxygen.
Finally, the reference cited above describes studies into the initiation of the polymerization of vinyl com-pounds by the dimethyl aniline/superpure oxygen/cobalt salt system. High-purity acrylonitrile, methyl methacrylate, ethyl acrylate and styrene can be polymerized with this system. The initiating reaction is interpreted as redox catalysis in which molecular oxygen acts as oxidizing agent. There are no references in the publication in question to the suitability of the multicomponent systems investigated for practical use in polymerization, and no such practical application is known to the present applicants, despite the availability of this reference for about twenty-five years.
It is an object of the present invention to provide a new class of activator systems which may be used in a new and simplified way for initiating the polymerization of olefinically unsaturated systems.
According to one aspect of the invention, a process of initiating the radical polymerization of olefinically unsaturated polymerizable components. The processcomprises rnixing the components with an activator system consisting essentially of:
~, .. ..
(a) from 30 to 60% by weight of a N-alkyl-substituted tertiary arylamine corresponding to formula I
R,~
= N - R3 (I) in which Rl is an unsubstituted or substituted aryl radical, R2 is an unsubstituted or substituted aryl radical or an unsubstituted or substituted, linear, or branched alkyl radical, and R3 is a substituted or unsubstituted linear or branched alkyl radical which has at least one H
atom in the a-position to the N;
(b) from 5 to 20% by weight of a metal compound which is soluble in said polymerizable components; and (c) from 30 to 60% by weight of a weakly acidic compound having a pKa value of at least about 0.9, all weights being based on the weight of said activator system, wherein the resultant mixture has an initial viscosity of at least between about 30 and about 100 mPa.s as measured at about 20 C with a Brookfield viscosimeter, and exposing the resulting ~ e to ambient air at room temperature or elevated temperature.
In another aspect of the invention, a filler may be added to the olefinically unsaturated polymerizable components prior to mixing the components with the activator system. In another embodiment, R1 is a phenyl radical and component (a) is an N, N-dialkyl-substituted aniline compound.
According to another aspect of the present invention, a moldable, radically-polymerizable, multi component mixture is provided. The mixture comprises olefinically unsaturated polymerizable components and an activator system consisting essentially of the three components (a), (b), and (c) described above.
In another aspect of the invention, component (c) of the mixture comprises at least one COOH group attached to preformed oligomer or polymer compounds.
~3 ~ ........
In yet another aspect of the invention, component (a) is kept separate from components (b) and (c) before mixing with the mixture of olefinically unsaturated polymerizable components.
Other and further aspects and advantages of the present invention will be apparent to those skilled in the art in view of the following detailed description.
Description of the Invention The new activator systems can be used to form mixtures wit~ olefinically unsaturated, poly~erizable components that do not polymerize in the absence of oxygen and water 3b _. ~
1338~97 are therefore stable in storage, either as one-part or multi-part adhesive systems. On the other hand, in a particularly important embodiment, these new adhesive systems can be activated, after a predictable time interval, usually called the ~pot life", by the action of water and oxygen always present in the ambient atmospheric air. Such adhesive systems will undergo time controlled hardening after the pot life has expired. In preferred embodiments, such activation occurs readily even at room temperature, although a moderate increase in temperature to as much as 30D C may sometimes be necessary.
In a first embodiment, the present invention includes radically polymerizable multicomponent mixtures that are sufficiently fluid to be shaped as desired, that are capable, simply by contact with ambient air at room temperature, of initiating radical polymerization of unsaturated molecules to produce time-controlled hardening after a predictable pot life, and that comprise, or preferably consist essentially of:
(A) ethylenically unsaturated, polymerizable molecules;
and (B) a polymerization initiator component that consists essentially of the following constituents:
(1) alkylaryl tertiary amine molecules containing at least one aliphatic N-C-H bond sequence;
(2) molecules of metal compounds at least partly soluble in the polymerizable multicomponent mixture and suitable to accelerate the drying of unsaturated oils; and (3) weakly acidic carboxylic acids, preferably having a pK~ value of at least 0.9;
and, optionally, (C) mechanical property modifiers, which may be solids or liquids, suitable for serving as filler, reinforce-ment, plasticizer, elasticizer or toughening agent, component of a polyblend, and/or the like in the polymer formed by polymerization of component (A);
1~38497 (D) dyes, pigments, or other coloring and/or opacifying agents; and (E) inhibitors of premature polymerization initiation, such as reducing agents, antioxidants, and radical scavengers.
As known to those skilled in the art, "pK~" means the negative of the logarithm to the base 10 of the ionization constant of the acid. By the statement that the metal compound is at least partly soluble in the polymerizable mixture, it is specifically meant that the solubility is at least 2 parts by weight per million ("ppm"), preferably at least 5 ppm, and more preferably at least 10 ppm.
In a second embodiment, the present invention includes the use of only the activator component described as item (B) above to initiate polymerization of other materials containing polymerizable unsaturation.
The invention is based on the observation that the problem stated above can be solved taking into account the elements described in detail in the following. Additional freedom in regard to practical application can be created by suitable auxiliary measures which are described in the following. Mere contact with air at ambient temperature or at most moderately elevated temperatures is sufficient to activate the starter system and, hence, to initiate the reaction in the system as a whole for dimensionally stable hardening. The open time of the system required for molding may be varied within wide limits.
Accordingly, the major point of novelty of the teaching according to the invention lies in the choice of the specific activator system which is being described for the first time in this combination. This combination differs from that described in the above reference by Horner in several ways, as set forth immediately below.
This invention is directed toward use under practical conditions. One particular requirement to be satisfied in this regard is that the catalyst systems active as so-called "autox" systems should be converted into the active state on contact not with pure and predried oxygen, but with ambient air with its comparatively limited oxygen content and the impurities always present, including moisture. For the purposes of practical application, the components to be polymerized are almost always present in admixture with fillers and/or other auxiliaries.
The present invention is based on observation that the problems stated above can be avoided by utilizing the components, and taking into account the factors, described in more detail below. Mere contact with air at ambient temperature or at most moderately elevated temperatures is sufficient to activate the initiator system and, hence, to initiate the reaction in the system as a whole for dimensionally stable hardening. The open time of the system required for molding or other shaping may be varied within wide limits through use of temporary inhibitors of the polymerization activating process, as further described hereinafter. Multicomponent systems having the composition according to the invention therefore have very broad and varied practical uses.
The three components of the activator system used in accordance with the invention will first be described in greater detail.
N-alkYl-substituted tert-arYlamines The amine components used in accordance with the invention preferably correspond in particular to general formula I:
Rl N-R3 (I), in which R1 is an aryl radical, which may be substituted but is attached to the nitrogen atoms via one of the carbon atoms in an aromatic nucleus; R2 may be any aryl or alkyl radical, which may be substituted and if alkyl may be linear or branched; and R3 is a linear or branched alkyl radical, which may also be substituted and which may be the same as or different from R2, but must contain at least one H atom present in the ~-position to the N.
The preferred aryl nucleus is that of benzene. The alkyl radicals present as R3 and optionally as R2 each preferably contains 10 or fewer, or in order of increasing preference 6 or fewer, 3 or fewer, and only one carbon atom(s). The methyl radical is most highly preferred. In a preferred embodiment, both R2 and R3 are alkyl or substituted alkyl radicals. Thus N,N-dialkyl-substituted aniline compounds, which may also be alkylated in the phenyl ring, are generally preferred. The most preferred components in the context of the invention are dimethyl aniline and, in particular, dimethyl-p-toluidine.
Basically, the principles stated by L. Horner et al, loc. cit., apply to the activity and the activatability of these tertiary amine compounds: nucleus substituents influence the autoxidation rate of the dimethyl aniline.
Electron donors increase the autoxidizability of the amine, while electrophilic substituents reduce it. Accordingly, p-toluidine compounds are more reactive than the otherwise structurally identical aniline derivatives. The general principles stated by Horner also apply with regard to the alkyl substituents in R3 and R2. The methyl group is much more accessible to oxidation than all other N-alkyl substituents. Basically, the known results of the action of dibenzoyl peroxide on tertiary amines, as reported in the cited literature reference, also apply here.
Metal compounds at least partly soluble in the system As already mentioned, the most important driers of the type in ~uestion are distinguished by the fact that, above all, metal compounds of a metal capable of occurring in several stable valences are used. Selected representatives of the transition metals can be particularly effective in this regard. The particular choice of the metal may have inter alia a velocity-determining effect on the initiation of polymerization, because of a dependence on temperature of the reactive intervention of this metal component in the 1338~97 -process as a whole. Components wh~ch are hiqhly active at room temperature are derived in particular from cobalt and/or manganese. Iron also has a certain, albeit weaker, effect in accelerating the reaction at room temperature.
5 The activity of other metal components, for example those based on vanadium, can be increased by increasing the temperature to such an extent that the polymerization reaction can be rapidly initiated.
Cobalt and/or manganese compounds, optionally in 10 admixture with other metallic components, such as compounds of lead, cerium, calcium, barium, zinc and/or zirconium, are particularly suitable for working at room temperature, which is of particular advantage for numerous applications.
Reference is made in this regard to the relevant specialist 15 literature, cf. for example the cited publication by Ullmann loc. cit. and the literature cited therein.
The metals in question here are used in the form of such compounds that they are at least partly soluble in the system as a whole. Both soap-like metal compounds and also 20 types otherwise bonded, particularly in complex form, to organic radicals are suitable. A typical example of work-ing in accordance with the teaching of the invention is the use of suitable metal naphthenates or metal acetyl acetonates. Provided that inorganic salts are sufficiently 25 soluble in the system, it is also possible to use them. A
typical example is iron chloride which has a distinctly accelerating effect when used in the system according to the invention.
It may be advisable to use the metal compounds in a 30 low valency stage of the metal, i.e. for example as cobalt (II) or manganese (II). In other cases, it is also suitable to use the metal compound in the higher valency stage of the metal. Thus, iron chloride, for example, is preferably used in the form of the Fe~3 salt.
For testing whether a particular metal compound is suitable for initiating polymerization according to this invention, it may be incorporated, to an extent of 0.01 part~ by weight of metal compound, into the following m~xture:
40 parts by weight of toluene, 10 parts by weight of triethyleneglycol dimethacrylate, 2 parts by weight of methacrylic acid, and 2 parts by weight of N,N-dimethyl-4-toluidine.
If the compound to be tested is not soluble in this mixture, it may first be dissolved in a suitable solvent and introduced in that form. If the metal compound is sufficiently active for use in this invention, the initially fluid mixture should gel within two hours of the introduction of the metal compound, in the presence of air.
Free weak carboxylic acid component A factor of crucial importance in the selection of these components is the acidity of the free carboxylic acid. The pK, value of the free acid should be no lower than about 0.9, the preferred lower limit being about 1.
If much more strongly acidic components are used, acceleration of the polymerization reaction comes to a stop. This is illustrated by the following examples. The PKa value of trichloroacetic acid is approximately 0.6. The addition of trichloroacetic acid in masked or unmasked form to the system destroys the ability of the multicomponent initiator system used in accordance with the invention to initiate polymerization reactions. By contrast, dichloro-acetic acid is a relatively weak carboxylic acid with a PK8 value of approximately 1.3. Thus dichloroacetic acid is eminently suitable for initiating polymerization reactions in accordance with the invention. Strongly acidic mineral acids, for example hydrochloric acid, destroy the ability of the activator systems used in accordance with the invention to initiate polymerization reactions. Acetic acid or derivatives hydrolyzable to acetic acid (the pK.
value of acetic acid being about 4.76) are eminently 3s suitable for accelerated reaction initiation according to this invention.
~ he preferable upper limit to the pK. value is in the region of very weakly acidic compounds, determined as free carboxylic acid. In numerical terms, therefore, the upper limit is at pK. values of approximately 13 and, preferably, at pK. values of approximately 11.5. ~owever, carboxylic acids which have pK. values in the hydrolyzed state of up to about 8 and preferably of up to about 6 or 7 are particu-larly suitable. Particularly effective components of the type in question here are thus derived from carboxylic acids which have pK. values in the hydrolyzed state in the range from about 1 to 6 or 7.
The carboxylic acids to be used in accordance with the invention may contain one or more carboxyl groups. The constitution of the acid as such is not a crucial parameter, given the correct pK. value. The compositions and systems according to the invention can advantageously be based on carboxylic acids containing 1 to 4 carboxyl groups and, in particular, 1 or 2 carboxyl groups.
The c~oice of the particular carboxylic acid is also largely determined by similar considerations of practical expediency. Readily obtainable carboxylic acids, such as lower aliphatic carboxylic acids or corresponding aromatic mono- or polybasic carboxylic acids are suitable compon-ents. Preferable aliphatic carboxylic acids are Cl18 and more preferably Cl10monocarboxylic acids, acetic acid again being particularly preferred. Preferable aromatic carbox-ylic acids are benzoic acid or corresponding polycarboxyl-ic acids, for example trimellitic or pyromellitic acid. As shown with reference to the example of dichloroacetic acid, substituted acids of this type are also suitable if their PKa value is within the stated limits.
In one embodiment of the invention, the free carboxyl-ic acids or carboxyl groups of the activator system are at least in part made up of COO~ groups attached to preformed oligomeric and/or polymeric compounds. These carboxyl groups may thus be utilized for several purposes in the context of the teaching according to the invention. In the polymerization initiation phase, these acid components per-form the described activating function. Quite apart fromthis, however, free carboxyl groups of the type in guestion can impart characteristic and sometimes desirable properties, in particular dimensional stability, to the hardened product. A possible coupling effect with respect to solid surfaces, for example of metal, or the increased reactivity towards alkaline media are also mentioned purely by way of example of benefits of the presence of acid groups attached to molecules incorporated into a polymer formed by activation according to this invention.
The free carboxyl groups in the oligomeric and/or polymeric components may be reactively bound into the dimensionally stable reaction product formed and/or may be present as non-reactive fillers in the hardened reaction product, depending on the particular structure of the oligomeric or polymeric additives.
The invention also encompasses this multifunctionality of acidic components used in a totally different way:
Radically initiated polymerization reactions may generally be carried out using ethylenically unsaturated free acids.
Such compounds as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and/or fumaric acid and also olefinically unsaturated compounds of the tetrahydro-phthalic acid type and related compounds are particularly well known as reactive mono- and/or di-carboxylic acids in this regard. Finally, however, it is also known that relatively long chain, mono- or poly-olefinically unsaturated carboxylic acids, particularly unsaturated fatty acids containing, for example, 10 to 30 carbon atoms and, preferably, 12 to 24 carbon atoms, can be included in radically initiated polymerization reactions through their content of ethylenic double bonds.
In the embodiment of the invention under discussion, acid components of the type in question are not only used as constituents of the reaction mixture hardening by polymerization, they are also able through their free acid groups at least partly to perform the acid function in the 1338~97 -activator system used in accordance with the invention of tertiary amine compound, metal compound, and weakly acidic component. It is clear that this provides for wide variation of the activator components to be used.
Activator systems of the three principal components described in the foregoing, namely aromatic amine compound, at least partly soluble metallic drier, and weak acid are able after taking up oxygen from the ambient air to initiate all the radically polymerizable, olefinically unsaturated systems which, hitherto, have been used with a variety of different, particularly peroxidic, starter systems. To this extent, the other constituents of the radically polymerizable, moldable multicomponent mixtures according to the invention may be any of those described in the extensive relevant literature which is concerned with polymerizing olefinically unsaturated radically polymerizable compounds. A very large number of possibilities of this type, tailored in their properties to the particular application envisaged, are currently known to those skilled in the art.
Polymerizable mixtures with at least moderately high viscosity values at the onset of the polymerization reac-tion are particularly suitable for the initiation of poly-merization in accordance with this invention, particularly at room temperature or only moderately higher temperature.
Tests have actually shown that contact with ambient air, even where a basically highly active combination of activating agents is used, does not lead to reaction initiation within a practical time, if at all, when highly mobile unsaturated materials are used, even where they are known per se for their high reactivity in the polymerization reaction~ Typical examples of such systems are conventionally stabilized lower acrylate esters, methacrylate esters, or styrene. An activator system of, for example, dimethyl-p-toluidine, soluble cobalt compounds and acetic acid hardens commercially available, unsaturated components of the type just; mentioned on contact with 13~8497 ..
ambient alr at room temperature only when the viscosity of the system a8 a whole is slightly greater than that obtained from the least viscous components alone.
Generally, therefore, radically polymerizable mixtures with an initial viscosity of at least about 30 to 100 mPa.s and preferably of at least about 200 or 300 mPa.s should be used in accordance with the invention. Particularly reliable initiation of the polymerization reaction can be expected in the case of mixtures which have an initial viscosity of at least about S00 mPa.s and, more especially, of at least about 1000 mPa.s. All these viscosity values are determined by a Brookfield viscosimeter.
Commercially available adhesive systems are known generally to have viscosities of at least about 3,000 mPa.s lS and more often up to about 10,000 mPa.s. Materials of this type are eminently suitable for processing in accordance with the invention. However, the invention is by no means limited to such materials. Considerably less viscous systems, for example spreadable paint systems used in par-ticular as solvent free surface coatings, are suitable forthe reaction-initiating mechanism described herein, provided that the above-mentioned minimum values for the initial viscosity of the material to be molded are observed. The same applies to other fields of application, for example the production of plastic moldings based on styrene/unsaturated polyester resins.
The necessary viscosity values may readily be obtained with mixtures which have an adequate content of oligomeric and/or polymeric components, optionally in admixture with low molecular weight, unsaturated components liquid at room temperature, such as (meth)acrylates. However, correspond-ingly viscous materials may also consist solely of pre-polymers or oligomers of suitable fluidity. The extensive knowledge of those skilled in the art about ethylenically unsaturated mixtures such as these hardenable by radical polymerization may be applied in this regard.
The multicomponent mixtures to be used in accordance * Trade Mark A
-13384g7 with the invention may be formulated as multi-part systems.
Before using the system, the components are mixed with one another in a known manner. The open pot life of the system may be regulated by suitable choice and adaptation of the principal components of the activator system, so that the starting reaction may be initiated and, hence, the system ultimately hardened under ambient conditions in air.
In one preferred example of multi-part embodiments of the invention, the three activator components are also separated into at least two parts, each of which may include polymerizable materials as well. The separated multiple parts are non-reactive, even on contact with air, until they are mixed together. Two part systems are the preferred type of multi-part systems, and in such two part systems, it is particularly preferred to separate the three main components of the activator systems used in accordance with the invention from one another in such a way that the tertiary amine compound is kept separate from the metal compounds and the free carboxylic acid. For use, these two separately stored components merely have to be mixed, molded or otherwise shaped as desired durinq the open pot life of the system, and brought into contact with ambient air.
The invention provides for the formulation of optimized active-substance mixtures. Without departing from the principles of the invention, it is possible to use insoluble fillers, polymeric thickeners, elasticizers, thickeners, thixotropic agents, piqments, couplinq agents, stabilizers, and the like without endangering the performance of the activator system according to the invention. This does of course require that interferences with the interaction of the activator components be precluded through the choice of the auxiliaries and fillers. General chemical knowledge may be applied this reqard.
One valuable feature of the multicomponent activator systems used in this invention is that additional 13~8~97 inhibition and hence control of the sy~tem as a whole i8 possible. Various mechanisms are available for inhibiting the "autox" system used in accordance with the invention, of which the three basic types 1 to 3 are listed below:
1. stabilization against 2 by addition of antioxidants 2. stabilization against R-OOH by addition of reducing agent 3. stabilization against radicals by addition of radical scavengers Typical stabilizer components are listed as follows, with the numbers in brackets after the particular compound indicating which of the three mechanisms listed above is to be expected from the stabilizer:
pyrogallol (l), 02-inhibited acrylates (l), hydroquinone (1,3), hydroquinone monomethyl ether (1,3), triphenyl phos-phine (2), tributyl phosphite (2), butyl hydroxytoluene (3), phenothiazine (3).
In the multiple component mixtures according to the invention that include polymerizable materials, the activator mixtures preferably make up no more than about 25% by weight and, more preferably, no more than about 10%
by weight, based on the weight of the mixture as a whole.
Depending on the activity of the components used, the weight of the activator mixture can be greatly reduced below these upper limits, for example to about 0.1% by weight or to at least about 0.5% by weight. Particularly preferable quantities of the activator system are at least about 1% by weight, preferably up to about 8% by weight and more preferably from about l to 7% by weight. All these figures are based on the one hand on the total weight of the polymerizable mixture according to the invention and the total weight of the three principal components of the activator system. When the invention is embodied in systems with more than part, the specified percentages are to be understood as those present after all parts of a particular system are mixed.
The three constituent classes of the activator system `_ are preferably used in the following quantitative ratios to one another (ln % by weight, based on the mixture of all the activator constituents): 0.5 to 20%, more preferably 5 to 15%, of the metal compound; 30 to 60%, more preferably 40 to 55%, of the tertiary amine compound; and 30 to 60%, more preferably 40 to 55%, of the weak acid.
The preferable quantities in which the metal compounds are used may also be defined by the ratio by weight of the weight of the metal to the weight of the three constituent activator system as follows: Preferred quantities of metal compound are from 0.01 to 5% by weight, more preferably from 0.05 to 2% by weight, and still more preferably from about 0.1 to 1% by weight metal, based on the total weight of the activator constituents.
If inhibitors and/or stabilizers of the type mentioned above are used to control the course of the reaction and/or the open pot life, the quantities in which they are used will be chosen according to their purpose. In each individual case, they may readily be determined by consid-erations known to those skilled in the art and/or by preliminary tests. The inhibitors used will normally not exceed a few percent, for example about 2 to 5% by weight, of the mixture as a whole and are generally used in quanti-ties of less than 1% by weight.
Mixtures of oligomers and/or polymers together with ethylenically unsaturated monomers of low molecular weight are used as mixtures of radically polmerizable materials for a variety of applications in practice generally. The mixture components of relatively high molecular weight are often at least partly dissolved in the monomers. Mixtures of this type are particularly suitable for processing in accordance with the invention. The content of monomers, for example (meth)acrylates, optionally substituted styrene and/or acrylonitrile, is generally at least 10% by weight, preferably at least 20% by weight and, in many applications, at least about 40% by weight, based on the final reactive mixture as a whole. In terms of weight, the -monomer component may be by far the predominant component so that, for example, 60 to 80% by weight of the mixture as a whole is formed by the low molecular weight monomers. As mentioned above, however, it is important to ensure that the mixture used has at least the minimum viscosity of the mixtures for reliable reaction initiation on contact with air, by the use of an adequate quantity of compounds of relatively high molecular weight and/or by other thickening agents.
Without any claim to completeness, the following examples of classes of suitable applications for this invention are mentioned here: aerobic adhesive systems, spreadable compositions for protective surface coatings, in particular solvent free lacquers and paints, and the production of moldings with initiation of polymerization by contact with ambient air, for example with styrene/
unsaturated polyester resins.
The practice of the invention may be further appreciated from the following non-limiting specific working examples.
E x a m p 1 e s Examples 1 - 9 These examples of two-part embodiments of the invention were all performed using parts with the two compositions shown below.
Part A Parts by Weight MMA (methyl methacrylate) 60 Polyacrylate (Plexigum~ MB 319, product of Rohm 30 used as a polymeric thickener) Cobalt acetyl acetonate 0.24 Acrylic acid 10 Part B
Plexigum MB 319 30 N,N-dimethyl-p-toluidine 10 Parts A and B were mixed in various quantitative ratios as '~ 1338~9~
shown below and the adhesive preparations thereby obtained were used to bond poly(vinyl chloride) plastic ("PVC~). To guarantee adequate oxygen uptake, each mixture was viqorously stirred in air for 1 minute and the substrates coated with the adhesive preparation were left in air for 2 minutes before being fitted together.
Example Weight Pot life Tensile shear strength, No. ratio A:B (mins.) newtons per square mm 1 9:1 11 1.0 2 8:2 11 1.4 3 7:s 12 1.4 4 6:4 12 MF at 1.7 5:5 13 MF at 1.9 6 4:6 13 MF at 3.2 7 3:7 16 MF at 2.5 8 2:8 20 MF at 2.5 9 1:9 36 MF at 3.6 MF = Tensile failure in the PVC material bonded rather than in the adhesive or at the interface.
Examples 10 - 19 These one part embodiments of the invention show the effects of variation of the amine concentration. Each mixture, which hardened spontaneously after contact with atmospheric oxygen, contained the amounts of N,N-dimethyl-p-toluidine shown below along with 6 g MMA
4 g Plexigum MB 319 0.5 g acetic acid and 0 50 mg of a solution of cobalt naphthenate in light mineral spirits, with 6% by weight Co.
1338~97 Example Quantity of Pot l~fe, Tensile shear strength, No. amine, wt % minutes newtons per square mm 1 13 3.1 (MF) S 11 2 12 8.1 (MF) 12 3 12 7.6 (MB) 13 4 11 4.7 (MB) 14 5 11 7.1 (MB) 6 10 8.5 (MB) 16 7 14 6.4 (MF) 17 8 14 7.6 (MB) 18 9 15 7.6 (MB) 19 10 13 5.8 (MB) Examples 20 - 29 These one part embodiments of the invention show the effects of some variation of the carboxylic acids and the polymerizable monomer mixtures used, as specified below.
Each embodiment, which hardened spontaneously after contact with atmospheric oxygen, contained 89.5 % by weight of polymerizable monomer(s) and 10.5 % by weight of an initiator component consisting of % N,N-dimethyl-p-toluidine 0.5 % cobalt naphthenate solution as for Examples 5 % carboxylic acid.
Example Monomer Carboxylic acid Pot life, No. minutes K 81)/MMA Acetic acid 10 21 n Propionic acid 11 22 n Chloroacetic acid 10 23 " Carboset~ 5152 90 24 MMA/PMMA3) Acetic acid 10 n AcryliC acid 9 26 n Dichloroacetic acid 12 27 Methacrylate- Acetic acid 2 terminated PUR ~Table continued on next page}
1~38~97 Example Monomer Carboxylic acid Pot life, No. minutes 28 THF-MA/PMMA" Acetic acid 11 29 MMA/PMMA Benzoic acid 25 ' A methacrylate-terminated polyester polyurethane (reaction product of CAPAT~ 200, a polycaprolactone manufactured by Union Carbide, with OH value 209, 2 moles; 2,4-tolylene diisocyanate, commercially available as DesmodurT~ T 100, a product of Bayer AG, 3 moles; B-01/20T~, a polypropylene glycol monobutyl ether manufactured by Hoechst, 1 mol; and hydroxyethyl methacrylate, 1 mole). This is mixed with an equal weight of methyl methacrylate.
2) An acrylic acid copolymer manufactured by B.F.
Goodrich, acid value 60 to 65.
3) A mixture of 60 parts MMA and 40 parts Plexigum MB 319 (a polyacrylate manufactured by Rohm) 20 4) A methacrylate-terminated polyurethane (reaction product of 1 mole each of B 01-20, toluene diisocyanate, and hydroxypropyl methacrylate) 5) A mixture of 2 parts tetrahydrofurfuryl methacrylate and 1 part Plexigum MB 319 Example 30 A mixture of 53 % MMA, % Plexigum MB 319, 4 % N,N-dimethyl-p-toluidine, 4 % acetic acid, and 3 % Mn(II) octanoate polymerizes 15 minutes after contact with atmospheric oxygen.
35 Examples 31 - 34 These one part embodiments of the invention illustrate variation of the amines used in the activator combination.
Each example except 32 used a mixture consisting of - 13~8~97 parts MMA, parts Plexigum MB 319, 3 parts acetic acid, 3 parts amine as shown below, and O.S part cobalt naphthenate.
For example 32, the mixture used 5 parts each of acid and amine but was otherwise the same.
Example Amine Pot life (mins.) 31 N,N-dimethyl aniline 60 32 N-ethyl-N-methyl aniline 47 33 N,N-dimethyl-m-toluidine 26 34 N,N-dimethyl-p-toluidine 18 Example 35 The following activator system: 5% acetic acid, S~
dimethyl-p-toluidine, 0.5% cobalt solution) was added to 89.5 % of the dimethacrylate of the condensate of bisphenol A with an average of 2 moles of ethylene oxide per mole of bisphenol. (This product is commercially available as DiacrylT~ 101 from AKZ0). There was no addition of thickener.
The pot life is 1 minute.
ExamPle 36 The activator mixture of Example 35 is added to the reaction product of bisphenol-A-diglycidyl ether with methacrylic acid (Rutapox 959, a product of Rutgers) with no addition of thickener.
The pot life is under 1 minute.
Example 37 The initiator system of Example 35 is added to Vestopal 150, a commercial product manufactured by Huls (unsaturated polyester resin, 66% in styrene), with no addition of thickener.
The pot life is 1.5 minutes.
Example 38 The following initiator system: 3% acetic acid, 3%
* Trade Mark 21 ~, A;
13~8497 dimethyl-p-toluidine, 0.5% cobalt solution, i8 added to a mixture of cyclohexyl methacrylate and Plexigum MB 319.
The pot life is 16 minutes.
and, optionally, (C) mechanical property modifiers, which may be solids or liquids, suitable for serving as filler, reinforce-ment, plasticizer, elasticizer or toughening agent, component of a polyblend, and/or the like in the polymer formed by polymerization of component (A);
1~38497 (D) dyes, pigments, or other coloring and/or opacifying agents; and (E) inhibitors of premature polymerization initiation, such as reducing agents, antioxidants, and radical scavengers.
As known to those skilled in the art, "pK~" means the negative of the logarithm to the base 10 of the ionization constant of the acid. By the statement that the metal compound is at least partly soluble in the polymerizable mixture, it is specifically meant that the solubility is at least 2 parts by weight per million ("ppm"), preferably at least 5 ppm, and more preferably at least 10 ppm.
In a second embodiment, the present invention includes the use of only the activator component described as item (B) above to initiate polymerization of other materials containing polymerizable unsaturation.
The invention is based on the observation that the problem stated above can be solved taking into account the elements described in detail in the following. Additional freedom in regard to practical application can be created by suitable auxiliary measures which are described in the following. Mere contact with air at ambient temperature or at most moderately elevated temperatures is sufficient to activate the starter system and, hence, to initiate the reaction in the system as a whole for dimensionally stable hardening. The open time of the system required for molding may be varied within wide limits.
Accordingly, the major point of novelty of the teaching according to the invention lies in the choice of the specific activator system which is being described for the first time in this combination. This combination differs from that described in the above reference by Horner in several ways, as set forth immediately below.
This invention is directed toward use under practical conditions. One particular requirement to be satisfied in this regard is that the catalyst systems active as so-called "autox" systems should be converted into the active state on contact not with pure and predried oxygen, but with ambient air with its comparatively limited oxygen content and the impurities always present, including moisture. For the purposes of practical application, the components to be polymerized are almost always present in admixture with fillers and/or other auxiliaries.
The present invention is based on observation that the problems stated above can be avoided by utilizing the components, and taking into account the factors, described in more detail below. Mere contact with air at ambient temperature or at most moderately elevated temperatures is sufficient to activate the initiator system and, hence, to initiate the reaction in the system as a whole for dimensionally stable hardening. The open time of the system required for molding or other shaping may be varied within wide limits through use of temporary inhibitors of the polymerization activating process, as further described hereinafter. Multicomponent systems having the composition according to the invention therefore have very broad and varied practical uses.
The three components of the activator system used in accordance with the invention will first be described in greater detail.
N-alkYl-substituted tert-arYlamines The amine components used in accordance with the invention preferably correspond in particular to general formula I:
Rl N-R3 (I), in which R1 is an aryl radical, which may be substituted but is attached to the nitrogen atoms via one of the carbon atoms in an aromatic nucleus; R2 may be any aryl or alkyl radical, which may be substituted and if alkyl may be linear or branched; and R3 is a linear or branched alkyl radical, which may also be substituted and which may be the same as or different from R2, but must contain at least one H atom present in the ~-position to the N.
The preferred aryl nucleus is that of benzene. The alkyl radicals present as R3 and optionally as R2 each preferably contains 10 or fewer, or in order of increasing preference 6 or fewer, 3 or fewer, and only one carbon atom(s). The methyl radical is most highly preferred. In a preferred embodiment, both R2 and R3 are alkyl or substituted alkyl radicals. Thus N,N-dialkyl-substituted aniline compounds, which may also be alkylated in the phenyl ring, are generally preferred. The most preferred components in the context of the invention are dimethyl aniline and, in particular, dimethyl-p-toluidine.
Basically, the principles stated by L. Horner et al, loc. cit., apply to the activity and the activatability of these tertiary amine compounds: nucleus substituents influence the autoxidation rate of the dimethyl aniline.
Electron donors increase the autoxidizability of the amine, while electrophilic substituents reduce it. Accordingly, p-toluidine compounds are more reactive than the otherwise structurally identical aniline derivatives. The general principles stated by Horner also apply with regard to the alkyl substituents in R3 and R2. The methyl group is much more accessible to oxidation than all other N-alkyl substituents. Basically, the known results of the action of dibenzoyl peroxide on tertiary amines, as reported in the cited literature reference, also apply here.
Metal compounds at least partly soluble in the system As already mentioned, the most important driers of the type in ~uestion are distinguished by the fact that, above all, metal compounds of a metal capable of occurring in several stable valences are used. Selected representatives of the transition metals can be particularly effective in this regard. The particular choice of the metal may have inter alia a velocity-determining effect on the initiation of polymerization, because of a dependence on temperature of the reactive intervention of this metal component in the 1338~97 -process as a whole. Components wh~ch are hiqhly active at room temperature are derived in particular from cobalt and/or manganese. Iron also has a certain, albeit weaker, effect in accelerating the reaction at room temperature.
5 The activity of other metal components, for example those based on vanadium, can be increased by increasing the temperature to such an extent that the polymerization reaction can be rapidly initiated.
Cobalt and/or manganese compounds, optionally in 10 admixture with other metallic components, such as compounds of lead, cerium, calcium, barium, zinc and/or zirconium, are particularly suitable for working at room temperature, which is of particular advantage for numerous applications.
Reference is made in this regard to the relevant specialist 15 literature, cf. for example the cited publication by Ullmann loc. cit. and the literature cited therein.
The metals in question here are used in the form of such compounds that they are at least partly soluble in the system as a whole. Both soap-like metal compounds and also 20 types otherwise bonded, particularly in complex form, to organic radicals are suitable. A typical example of work-ing in accordance with the teaching of the invention is the use of suitable metal naphthenates or metal acetyl acetonates. Provided that inorganic salts are sufficiently 25 soluble in the system, it is also possible to use them. A
typical example is iron chloride which has a distinctly accelerating effect when used in the system according to the invention.
It may be advisable to use the metal compounds in a 30 low valency stage of the metal, i.e. for example as cobalt (II) or manganese (II). In other cases, it is also suitable to use the metal compound in the higher valency stage of the metal. Thus, iron chloride, for example, is preferably used in the form of the Fe~3 salt.
For testing whether a particular metal compound is suitable for initiating polymerization according to this invention, it may be incorporated, to an extent of 0.01 part~ by weight of metal compound, into the following m~xture:
40 parts by weight of toluene, 10 parts by weight of triethyleneglycol dimethacrylate, 2 parts by weight of methacrylic acid, and 2 parts by weight of N,N-dimethyl-4-toluidine.
If the compound to be tested is not soluble in this mixture, it may first be dissolved in a suitable solvent and introduced in that form. If the metal compound is sufficiently active for use in this invention, the initially fluid mixture should gel within two hours of the introduction of the metal compound, in the presence of air.
Free weak carboxylic acid component A factor of crucial importance in the selection of these components is the acidity of the free carboxylic acid. The pK, value of the free acid should be no lower than about 0.9, the preferred lower limit being about 1.
If much more strongly acidic components are used, acceleration of the polymerization reaction comes to a stop. This is illustrated by the following examples. The PKa value of trichloroacetic acid is approximately 0.6. The addition of trichloroacetic acid in masked or unmasked form to the system destroys the ability of the multicomponent initiator system used in accordance with the invention to initiate polymerization reactions. By contrast, dichloro-acetic acid is a relatively weak carboxylic acid with a PK8 value of approximately 1.3. Thus dichloroacetic acid is eminently suitable for initiating polymerization reactions in accordance with the invention. Strongly acidic mineral acids, for example hydrochloric acid, destroy the ability of the activator systems used in accordance with the invention to initiate polymerization reactions. Acetic acid or derivatives hydrolyzable to acetic acid (the pK.
value of acetic acid being about 4.76) are eminently 3s suitable for accelerated reaction initiation according to this invention.
~ he preferable upper limit to the pK. value is in the region of very weakly acidic compounds, determined as free carboxylic acid. In numerical terms, therefore, the upper limit is at pK. values of approximately 13 and, preferably, at pK. values of approximately 11.5. ~owever, carboxylic acids which have pK. values in the hydrolyzed state of up to about 8 and preferably of up to about 6 or 7 are particu-larly suitable. Particularly effective components of the type in question here are thus derived from carboxylic acids which have pK. values in the hydrolyzed state in the range from about 1 to 6 or 7.
The carboxylic acids to be used in accordance with the invention may contain one or more carboxyl groups. The constitution of the acid as such is not a crucial parameter, given the correct pK. value. The compositions and systems according to the invention can advantageously be based on carboxylic acids containing 1 to 4 carboxyl groups and, in particular, 1 or 2 carboxyl groups.
The c~oice of the particular carboxylic acid is also largely determined by similar considerations of practical expediency. Readily obtainable carboxylic acids, such as lower aliphatic carboxylic acids or corresponding aromatic mono- or polybasic carboxylic acids are suitable compon-ents. Preferable aliphatic carboxylic acids are Cl18 and more preferably Cl10monocarboxylic acids, acetic acid again being particularly preferred. Preferable aromatic carbox-ylic acids are benzoic acid or corresponding polycarboxyl-ic acids, for example trimellitic or pyromellitic acid. As shown with reference to the example of dichloroacetic acid, substituted acids of this type are also suitable if their PKa value is within the stated limits.
In one embodiment of the invention, the free carboxyl-ic acids or carboxyl groups of the activator system are at least in part made up of COO~ groups attached to preformed oligomeric and/or polymeric compounds. These carboxyl groups may thus be utilized for several purposes in the context of the teaching according to the invention. In the polymerization initiation phase, these acid components per-form the described activating function. Quite apart fromthis, however, free carboxyl groups of the type in guestion can impart characteristic and sometimes desirable properties, in particular dimensional stability, to the hardened product. A possible coupling effect with respect to solid surfaces, for example of metal, or the increased reactivity towards alkaline media are also mentioned purely by way of example of benefits of the presence of acid groups attached to molecules incorporated into a polymer formed by activation according to this invention.
The free carboxyl groups in the oligomeric and/or polymeric components may be reactively bound into the dimensionally stable reaction product formed and/or may be present as non-reactive fillers in the hardened reaction product, depending on the particular structure of the oligomeric or polymeric additives.
The invention also encompasses this multifunctionality of acidic components used in a totally different way:
Radically initiated polymerization reactions may generally be carried out using ethylenically unsaturated free acids.
Such compounds as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and/or fumaric acid and also olefinically unsaturated compounds of the tetrahydro-phthalic acid type and related compounds are particularly well known as reactive mono- and/or di-carboxylic acids in this regard. Finally, however, it is also known that relatively long chain, mono- or poly-olefinically unsaturated carboxylic acids, particularly unsaturated fatty acids containing, for example, 10 to 30 carbon atoms and, preferably, 12 to 24 carbon atoms, can be included in radically initiated polymerization reactions through their content of ethylenic double bonds.
In the embodiment of the invention under discussion, acid components of the type in question are not only used as constituents of the reaction mixture hardening by polymerization, they are also able through their free acid groups at least partly to perform the acid function in the 1338~97 -activator system used in accordance with the invention of tertiary amine compound, metal compound, and weakly acidic component. It is clear that this provides for wide variation of the activator components to be used.
Activator systems of the three principal components described in the foregoing, namely aromatic amine compound, at least partly soluble metallic drier, and weak acid are able after taking up oxygen from the ambient air to initiate all the radically polymerizable, olefinically unsaturated systems which, hitherto, have been used with a variety of different, particularly peroxidic, starter systems. To this extent, the other constituents of the radically polymerizable, moldable multicomponent mixtures according to the invention may be any of those described in the extensive relevant literature which is concerned with polymerizing olefinically unsaturated radically polymerizable compounds. A very large number of possibilities of this type, tailored in their properties to the particular application envisaged, are currently known to those skilled in the art.
Polymerizable mixtures with at least moderately high viscosity values at the onset of the polymerization reac-tion are particularly suitable for the initiation of poly-merization in accordance with this invention, particularly at room temperature or only moderately higher temperature.
Tests have actually shown that contact with ambient air, even where a basically highly active combination of activating agents is used, does not lead to reaction initiation within a practical time, if at all, when highly mobile unsaturated materials are used, even where they are known per se for their high reactivity in the polymerization reaction~ Typical examples of such systems are conventionally stabilized lower acrylate esters, methacrylate esters, or styrene. An activator system of, for example, dimethyl-p-toluidine, soluble cobalt compounds and acetic acid hardens commercially available, unsaturated components of the type just; mentioned on contact with 13~8497 ..
ambient alr at room temperature only when the viscosity of the system a8 a whole is slightly greater than that obtained from the least viscous components alone.
Generally, therefore, radically polymerizable mixtures with an initial viscosity of at least about 30 to 100 mPa.s and preferably of at least about 200 or 300 mPa.s should be used in accordance with the invention. Particularly reliable initiation of the polymerization reaction can be expected in the case of mixtures which have an initial viscosity of at least about S00 mPa.s and, more especially, of at least about 1000 mPa.s. All these viscosity values are determined by a Brookfield viscosimeter.
Commercially available adhesive systems are known generally to have viscosities of at least about 3,000 mPa.s lS and more often up to about 10,000 mPa.s. Materials of this type are eminently suitable for processing in accordance with the invention. However, the invention is by no means limited to such materials. Considerably less viscous systems, for example spreadable paint systems used in par-ticular as solvent free surface coatings, are suitable forthe reaction-initiating mechanism described herein, provided that the above-mentioned minimum values for the initial viscosity of the material to be molded are observed. The same applies to other fields of application, for example the production of plastic moldings based on styrene/unsaturated polyester resins.
The necessary viscosity values may readily be obtained with mixtures which have an adequate content of oligomeric and/or polymeric components, optionally in admixture with low molecular weight, unsaturated components liquid at room temperature, such as (meth)acrylates. However, correspond-ingly viscous materials may also consist solely of pre-polymers or oligomers of suitable fluidity. The extensive knowledge of those skilled in the art about ethylenically unsaturated mixtures such as these hardenable by radical polymerization may be applied in this regard.
The multicomponent mixtures to be used in accordance * Trade Mark A
-13384g7 with the invention may be formulated as multi-part systems.
Before using the system, the components are mixed with one another in a known manner. The open pot life of the system may be regulated by suitable choice and adaptation of the principal components of the activator system, so that the starting reaction may be initiated and, hence, the system ultimately hardened under ambient conditions in air.
In one preferred example of multi-part embodiments of the invention, the three activator components are also separated into at least two parts, each of which may include polymerizable materials as well. The separated multiple parts are non-reactive, even on contact with air, until they are mixed together. Two part systems are the preferred type of multi-part systems, and in such two part systems, it is particularly preferred to separate the three main components of the activator systems used in accordance with the invention from one another in such a way that the tertiary amine compound is kept separate from the metal compounds and the free carboxylic acid. For use, these two separately stored components merely have to be mixed, molded or otherwise shaped as desired durinq the open pot life of the system, and brought into contact with ambient air.
The invention provides for the formulation of optimized active-substance mixtures. Without departing from the principles of the invention, it is possible to use insoluble fillers, polymeric thickeners, elasticizers, thickeners, thixotropic agents, piqments, couplinq agents, stabilizers, and the like without endangering the performance of the activator system according to the invention. This does of course require that interferences with the interaction of the activator components be precluded through the choice of the auxiliaries and fillers. General chemical knowledge may be applied this reqard.
One valuable feature of the multicomponent activator systems used in this invention is that additional 13~8~97 inhibition and hence control of the sy~tem as a whole i8 possible. Various mechanisms are available for inhibiting the "autox" system used in accordance with the invention, of which the three basic types 1 to 3 are listed below:
1. stabilization against 2 by addition of antioxidants 2. stabilization against R-OOH by addition of reducing agent 3. stabilization against radicals by addition of radical scavengers Typical stabilizer components are listed as follows, with the numbers in brackets after the particular compound indicating which of the three mechanisms listed above is to be expected from the stabilizer:
pyrogallol (l), 02-inhibited acrylates (l), hydroquinone (1,3), hydroquinone monomethyl ether (1,3), triphenyl phos-phine (2), tributyl phosphite (2), butyl hydroxytoluene (3), phenothiazine (3).
In the multiple component mixtures according to the invention that include polymerizable materials, the activator mixtures preferably make up no more than about 25% by weight and, more preferably, no more than about 10%
by weight, based on the weight of the mixture as a whole.
Depending on the activity of the components used, the weight of the activator mixture can be greatly reduced below these upper limits, for example to about 0.1% by weight or to at least about 0.5% by weight. Particularly preferable quantities of the activator system are at least about 1% by weight, preferably up to about 8% by weight and more preferably from about l to 7% by weight. All these figures are based on the one hand on the total weight of the polymerizable mixture according to the invention and the total weight of the three principal components of the activator system. When the invention is embodied in systems with more than part, the specified percentages are to be understood as those present after all parts of a particular system are mixed.
The three constituent classes of the activator system `_ are preferably used in the following quantitative ratios to one another (ln % by weight, based on the mixture of all the activator constituents): 0.5 to 20%, more preferably 5 to 15%, of the metal compound; 30 to 60%, more preferably 40 to 55%, of the tertiary amine compound; and 30 to 60%, more preferably 40 to 55%, of the weak acid.
The preferable quantities in which the metal compounds are used may also be defined by the ratio by weight of the weight of the metal to the weight of the three constituent activator system as follows: Preferred quantities of metal compound are from 0.01 to 5% by weight, more preferably from 0.05 to 2% by weight, and still more preferably from about 0.1 to 1% by weight metal, based on the total weight of the activator constituents.
If inhibitors and/or stabilizers of the type mentioned above are used to control the course of the reaction and/or the open pot life, the quantities in which they are used will be chosen according to their purpose. In each individual case, they may readily be determined by consid-erations known to those skilled in the art and/or by preliminary tests. The inhibitors used will normally not exceed a few percent, for example about 2 to 5% by weight, of the mixture as a whole and are generally used in quanti-ties of less than 1% by weight.
Mixtures of oligomers and/or polymers together with ethylenically unsaturated monomers of low molecular weight are used as mixtures of radically polmerizable materials for a variety of applications in practice generally. The mixture components of relatively high molecular weight are often at least partly dissolved in the monomers. Mixtures of this type are particularly suitable for processing in accordance with the invention. The content of monomers, for example (meth)acrylates, optionally substituted styrene and/or acrylonitrile, is generally at least 10% by weight, preferably at least 20% by weight and, in many applications, at least about 40% by weight, based on the final reactive mixture as a whole. In terms of weight, the -monomer component may be by far the predominant component so that, for example, 60 to 80% by weight of the mixture as a whole is formed by the low molecular weight monomers. As mentioned above, however, it is important to ensure that the mixture used has at least the minimum viscosity of the mixtures for reliable reaction initiation on contact with air, by the use of an adequate quantity of compounds of relatively high molecular weight and/or by other thickening agents.
Without any claim to completeness, the following examples of classes of suitable applications for this invention are mentioned here: aerobic adhesive systems, spreadable compositions for protective surface coatings, in particular solvent free lacquers and paints, and the production of moldings with initiation of polymerization by contact with ambient air, for example with styrene/
unsaturated polyester resins.
The practice of the invention may be further appreciated from the following non-limiting specific working examples.
E x a m p 1 e s Examples 1 - 9 These examples of two-part embodiments of the invention were all performed using parts with the two compositions shown below.
Part A Parts by Weight MMA (methyl methacrylate) 60 Polyacrylate (Plexigum~ MB 319, product of Rohm 30 used as a polymeric thickener) Cobalt acetyl acetonate 0.24 Acrylic acid 10 Part B
Plexigum MB 319 30 N,N-dimethyl-p-toluidine 10 Parts A and B were mixed in various quantitative ratios as '~ 1338~9~
shown below and the adhesive preparations thereby obtained were used to bond poly(vinyl chloride) plastic ("PVC~). To guarantee adequate oxygen uptake, each mixture was viqorously stirred in air for 1 minute and the substrates coated with the adhesive preparation were left in air for 2 minutes before being fitted together.
Example Weight Pot life Tensile shear strength, No. ratio A:B (mins.) newtons per square mm 1 9:1 11 1.0 2 8:2 11 1.4 3 7:s 12 1.4 4 6:4 12 MF at 1.7 5:5 13 MF at 1.9 6 4:6 13 MF at 3.2 7 3:7 16 MF at 2.5 8 2:8 20 MF at 2.5 9 1:9 36 MF at 3.6 MF = Tensile failure in the PVC material bonded rather than in the adhesive or at the interface.
Examples 10 - 19 These one part embodiments of the invention show the effects of variation of the amine concentration. Each mixture, which hardened spontaneously after contact with atmospheric oxygen, contained the amounts of N,N-dimethyl-p-toluidine shown below along with 6 g MMA
4 g Plexigum MB 319 0.5 g acetic acid and 0 50 mg of a solution of cobalt naphthenate in light mineral spirits, with 6% by weight Co.
1338~97 Example Quantity of Pot l~fe, Tensile shear strength, No. amine, wt % minutes newtons per square mm 1 13 3.1 (MF) S 11 2 12 8.1 (MF) 12 3 12 7.6 (MB) 13 4 11 4.7 (MB) 14 5 11 7.1 (MB) 6 10 8.5 (MB) 16 7 14 6.4 (MF) 17 8 14 7.6 (MB) 18 9 15 7.6 (MB) 19 10 13 5.8 (MB) Examples 20 - 29 These one part embodiments of the invention show the effects of some variation of the carboxylic acids and the polymerizable monomer mixtures used, as specified below.
Each embodiment, which hardened spontaneously after contact with atmospheric oxygen, contained 89.5 % by weight of polymerizable monomer(s) and 10.5 % by weight of an initiator component consisting of % N,N-dimethyl-p-toluidine 0.5 % cobalt naphthenate solution as for Examples 5 % carboxylic acid.
Example Monomer Carboxylic acid Pot life, No. minutes K 81)/MMA Acetic acid 10 21 n Propionic acid 11 22 n Chloroacetic acid 10 23 " Carboset~ 5152 90 24 MMA/PMMA3) Acetic acid 10 n AcryliC acid 9 26 n Dichloroacetic acid 12 27 Methacrylate- Acetic acid 2 terminated PUR ~Table continued on next page}
1~38~97 Example Monomer Carboxylic acid Pot life, No. minutes 28 THF-MA/PMMA" Acetic acid 11 29 MMA/PMMA Benzoic acid 25 ' A methacrylate-terminated polyester polyurethane (reaction product of CAPAT~ 200, a polycaprolactone manufactured by Union Carbide, with OH value 209, 2 moles; 2,4-tolylene diisocyanate, commercially available as DesmodurT~ T 100, a product of Bayer AG, 3 moles; B-01/20T~, a polypropylene glycol monobutyl ether manufactured by Hoechst, 1 mol; and hydroxyethyl methacrylate, 1 mole). This is mixed with an equal weight of methyl methacrylate.
2) An acrylic acid copolymer manufactured by B.F.
Goodrich, acid value 60 to 65.
3) A mixture of 60 parts MMA and 40 parts Plexigum MB 319 (a polyacrylate manufactured by Rohm) 20 4) A methacrylate-terminated polyurethane (reaction product of 1 mole each of B 01-20, toluene diisocyanate, and hydroxypropyl methacrylate) 5) A mixture of 2 parts tetrahydrofurfuryl methacrylate and 1 part Plexigum MB 319 Example 30 A mixture of 53 % MMA, % Plexigum MB 319, 4 % N,N-dimethyl-p-toluidine, 4 % acetic acid, and 3 % Mn(II) octanoate polymerizes 15 minutes after contact with atmospheric oxygen.
35 Examples 31 - 34 These one part embodiments of the invention illustrate variation of the amines used in the activator combination.
Each example except 32 used a mixture consisting of - 13~8~97 parts MMA, parts Plexigum MB 319, 3 parts acetic acid, 3 parts amine as shown below, and O.S part cobalt naphthenate.
For example 32, the mixture used 5 parts each of acid and amine but was otherwise the same.
Example Amine Pot life (mins.) 31 N,N-dimethyl aniline 60 32 N-ethyl-N-methyl aniline 47 33 N,N-dimethyl-m-toluidine 26 34 N,N-dimethyl-p-toluidine 18 Example 35 The following activator system: 5% acetic acid, S~
dimethyl-p-toluidine, 0.5% cobalt solution) was added to 89.5 % of the dimethacrylate of the condensate of bisphenol A with an average of 2 moles of ethylene oxide per mole of bisphenol. (This product is commercially available as DiacrylT~ 101 from AKZ0). There was no addition of thickener.
The pot life is 1 minute.
ExamPle 36 The activator mixture of Example 35 is added to the reaction product of bisphenol-A-diglycidyl ether with methacrylic acid (Rutapox 959, a product of Rutgers) with no addition of thickener.
The pot life is under 1 minute.
Example 37 The initiator system of Example 35 is added to Vestopal 150, a commercial product manufactured by Huls (unsaturated polyester resin, 66% in styrene), with no addition of thickener.
The pot life is 1.5 minutes.
Example 38 The following initiator system: 3% acetic acid, 3%
* Trade Mark 21 ~, A;
13~8497 dimethyl-p-toluidine, 0.5% cobalt solution, i8 added to a mixture of cyclohexyl methacrylate and Plexigum MB 319.
The pot life is 16 minutes.
Claims (18)
1. The process of initiating the radical polymerization of olefinically unsaturated polymerizable components comprising mixing said components with an activator system consisting essentially of (a) from 30 to 60% by weight of a N-alkyl-substituted tertiary arylamine corresponding to formula I
(I) in which R1 is an unsubstituted or substituted aryl radical, R2 is an unsubstituted or substituted aryl radical or an unsubstituted or substituted, linear, or branched alkyl radical, and R3 is a substituted or unsubstituted linear or branched alkyl radical which has at least one H atom in the .alpha.-position to the N;
(b) from 5 to 20% by weight of a metal compound which is soluble in said polymerizable components; and (c) from 30 to 60% by weight of a weakly acidic compound having a pKa value of at least about 0.9, all weights being based on the weight of said activator system, wherein the resultant mixture has an initial viscosity of at least between about 30 and about 100 mPa.s as measured at about 20°C with a Brookfield viscosimeter, and exposing the resulting mixture to ambient air at room temperature or elevated temperature.
(I) in which R1 is an unsubstituted or substituted aryl radical, R2 is an unsubstituted or substituted aryl radical or an unsubstituted or substituted, linear, or branched alkyl radical, and R3 is a substituted or unsubstituted linear or branched alkyl radical which has at least one H atom in the .alpha.-position to the N;
(b) from 5 to 20% by weight of a metal compound which is soluble in said polymerizable components; and (c) from 30 to 60% by weight of a weakly acidic compound having a pKa value of at least about 0.9, all weights being based on the weight of said activator system, wherein the resultant mixture has an initial viscosity of at least between about 30 and about 100 mPa.s as measured at about 20°C with a Brookfield viscosimeter, and exposing the resulting mixture to ambient air at room temperature or elevated temperature.
2. The process as in claim 1 wherein said olefinically unsaturated polymerizable components have an initial viscosity of at least about 30 mPa.s.
3. The process as in claim 1 including adding a filler to said olefinically unsaturated polymerizable components prior to mixing said components with said activator system.
4. The process as in claim l wherein R1 is a phenyl radical and said component (a) is an N, N-dialkyl-substituted aniline compound.
5. The process as in claim 4 wherein said component (a) is selected from the group consisting of dimethyl aniline and dimethyl-p-toluidine.
6. The process as in claim 1 wherein said component (b) is present in more than one valency state.
7. The process as in claim 1 wherein said metal compound contains a transition metal selected from the group consisting of cobalt, manganese, iron and vanadium.
8. The process as in claim 1 wherein said component (c) has a pKa value of up to about 13.
9. The process as in claim 1 wherein said component (c) comprises a carboxylic acid containing 1 to 4 carboxyl groups.
10. The process as in claim 1 wherein said olefinically unsaturated polymerizable components are selected from the group consisting of acrylates, methacrylates, styrene, substituted styrene and acrylonitrile-containing compounds.
11. The process as in claim 1 including adding to said olefinically unsaturated polymerizable components a material selected from the group consisting of thickener, plasticizer, pigment, coupling agent, stabilizer, anti-oxidant, reducing agent and radical inhibitor.
12. The process as in claim 1 wherein said activator system is present in an amount of up to about 25%/wt, based on the weight of said resultant mixture.
13. The process as in claim 1 wherein said olefinically unsaturated components contain at least about 20% by weight of monomers, based on the weight of said resultant mixture.
14. A moldable, radically-polymerizable, multi-component mixture comprising olefinically unsaturated polymerizable components and an activator system consisting essentially of (a) from 30 to 60% by weight of a N-alkyl-substituted tertiary arylamine corresponding to formula I
(I) in which R1 is an unsubstituted or substituted aryl radical, R2 is an unsubstituted or substituted aryl radical or an unsubstituted or substituted, linear, or branched alkyl radical, and R3 is a substituted or unsubstituted linear or branched alkyl radical which has at least one H atom in the .alpha.-position to the N;
(b) from 5 to 20% by weight of a metal compound which is soluble in said polymerizable components; and (c) from 30 to 60% by weight of a weakly acidic compound having a pKa value of at least about 0.9, all weights being based on the weight of said activator system, wherein said activator system is initiated by contact with ambient air.
(I) in which R1 is an unsubstituted or substituted aryl radical, R2 is an unsubstituted or substituted aryl radical or an unsubstituted or substituted, linear, or branched alkyl radical, and R3 is a substituted or unsubstituted linear or branched alkyl radical which has at least one H atom in the .alpha.-position to the N;
(b) from 5 to 20% by weight of a metal compound which is soluble in said polymerizable components; and (c) from 30 to 60% by weight of a weakly acidic compound having a pKa value of at least about 0.9, all weights being based on the weight of said activator system, wherein said activator system is initiated by contact with ambient air.
15. A mixture as in claim 14 having an initial viscosity of at least between about 30 and about 100 mPa.s as measured at about 20°C with a Brookfield viscosimeter.
16. A mixture as in claim 14 wherein said component (c) comprises an ethylenically unsaturated mono- or di-carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid.
17. A mixture as in claim 14 wherein said component (c) comprises at least one COOH group attached to preformed oligomer or polymer compounds.
18. A mixture as in claim 14 wherein said component (a) is kept separate from said components (b) and (c) before mixing with said mixture of olefinically unsaturated polymerizable components.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3829461.3 | 1988-08-31 | ||
| DE3829461A DE3829461A1 (en) | 1988-08-31 | 1988-08-31 | NEW RADICALLY POLYMERIZABLE MULTIPURPOSE MIXTURES AND THEIR USE (II) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1338497C true CA1338497C (en) | 1996-07-30 |
Family
ID=6361931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000610029A Expired - Fee Related CA1338497C (en) | 1988-08-31 | 1989-08-31 | Latent polymerization initiator composition that is activated, after a delay time, by contact with air, and uses of such compositions |
Country Status (14)
| Country | Link |
|---|---|
| EP (2) | EP0431013A1 (en) |
| JP (1) | JP2763809B2 (en) |
| KR (1) | KR0146957B1 (en) |
| AT (1) | ATE106903T1 (en) |
| AU (1) | AU625641B2 (en) |
| BR (1) | BR8907628A (en) |
| CA (1) | CA1338497C (en) |
| DE (2) | DE3829461A1 (en) |
| ES (1) | ES2054959T3 (en) |
| HK (1) | HK138095A (en) |
| IE (1) | IE64312B1 (en) |
| MX (1) | MX170330B (en) |
| WO (1) | WO1990002142A1 (en) |
| ZA (1) | ZA896647B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4420151A1 (en) * | 1994-06-09 | 1995-12-14 | Henkel Kgaa | One-component reactive adhesive |
| DE19501933A1 (en) * | 1995-01-24 | 1996-07-25 | Henkel Kgaa | Aerobically curable adhesive |
| EP2492329B1 (en) * | 2011-02-22 | 2015-02-11 | Sika Technology AG | (Meth)acrylic composition with reduced surface tackiness |
| EP2706093A1 (en) * | 2012-09-05 | 2014-03-12 | Sika Technology AG | Adhesive compound for polyolefinic membranes |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE581239A (en) * | 1958-08-05 | 1900-01-01 |
-
1988
- 1988-08-31 DE DE3829461A patent/DE3829461A1/en not_active Withdrawn
-
1989
- 1989-08-22 EP EP89909563A patent/EP0431013A1/en active Pending
- 1989-08-22 AT AT89115432T patent/ATE106903T1/en not_active IP Right Cessation
- 1989-08-22 BR BR898907628A patent/BR8907628A/en not_active Application Discontinuation
- 1989-08-22 WO PCT/EP1989/000980 patent/WO1990002142A1/en not_active Application Discontinuation
- 1989-08-22 ES ES89115432T patent/ES2054959T3/en not_active Expired - Lifetime
- 1989-08-22 KR KR1019900700897A patent/KR0146957B1/en not_active IP Right Cessation
- 1989-08-22 JP JP1508959A patent/JP2763809B2/en not_active Expired - Lifetime
- 1989-08-22 DE DE58907817T patent/DE58907817D1/en not_active Expired - Fee Related
- 1989-08-22 EP EP89115432A patent/EP0358033B1/en not_active Expired - Lifetime
- 1989-08-22 AU AU41825/89A patent/AU625641B2/en not_active Ceased
- 1989-08-29 MX MX017342A patent/MX170330B/en unknown
- 1989-08-30 IE IE278189A patent/IE64312B1/en not_active IP Right Cessation
- 1989-08-30 ZA ZA896647A patent/ZA896647B/en unknown
- 1989-08-31 CA CA000610029A patent/CA1338497C/en not_active Expired - Fee Related
-
1995
- 1995-08-31 HK HK138095A patent/HK138095A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ATE106903T1 (en) | 1994-06-15 |
| IE64312B1 (en) | 1995-07-26 |
| HK138095A (en) | 1995-09-08 |
| AU4182589A (en) | 1990-03-23 |
| ZA896647B (en) | 1990-07-25 |
| EP0431013A1 (en) | 1991-06-12 |
| JPH04500226A (en) | 1992-01-16 |
| BR8907628A (en) | 1991-07-30 |
| KR0146957B1 (en) | 1998-08-17 |
| KR900701855A (en) | 1990-12-04 |
| JP2763809B2 (en) | 1998-06-11 |
| AU625641B2 (en) | 1992-07-16 |
| DE3829461A1 (en) | 1990-04-26 |
| EP0358033A1 (en) | 1990-03-14 |
| IE892781L (en) | 1990-02-28 |
| ES2054959T3 (en) | 1994-08-16 |
| DE58907817D1 (en) | 1994-07-14 |
| EP0358033B1 (en) | 1994-06-08 |
| WO1990002142A1 (en) | 1990-03-08 |
| MX170330B (en) | 1993-08-16 |
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